Methods of fabricating nano-gap electrode structures in array configurations, and the structures so produced. The fabrication method involves depositing first and second pluralities of electrodes comprising nanowires using processes such as lithography, deposition of metals, lift-off processes, and chemical etching that can be performed using conventional processing tools applicable to electronic materials processing. The gap spacing in the nano-gap electrode array is defined by the thickness of a sacrificial spacer layer that is deposited between the first and second pluralities of electrodes. The sacrificial spacer layer is removed by etching, thereby leaving a structure in which the distance between pairs of electrodes is substantially equal to the thickness of the sacrificial spacer layer. Electrode arrays with gaps measured in units of nanometers are produced. In one embodiment, the first and second pluralities of electrodes are aligned in mutually orthogonal orientations.